Cyclic silazanes containing an oxamido ester group and methods

ABSTRACT

Cyclic silazanes containing an oxamido ester group and methods of making these compounds are described. The compounds can be used, for example, to make oxamido ester-terminated siloxanes, which can be precursors for the preparation of various polymeric materials such as, for example, polydiorganosiloxane polyoxamides.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 11/821,571, filed Jun.22, 2007, now allowed, the disclosure of which is incorporated byreferenced in its entirety herein.

TECHNICAL FIELD

Cyclic silazanes containing an oxamido ester group and methods of makingand using these compounds are described.

BACKGROUND

Siloxane polymers have unique properties derived mainly from thephysical and chemical characteristics of the siloxane bond. Theseproperties include low glass transition temperature, thermal andoxidative stability, resistance to ultraviolet radiation, low surfaceenergy and hydrophobicity, high permeability to many gases, andbiocompatibility. The siloxane polymers, however, often lack tensilestrength.

The low tensile strength of the siloxane polymers can be improved byforming block copolymers. Some block copolymers contain a “soft”siloxane polymeric block or segment and any of a variety of “hard”blocks or segments. Exemplary block copolymers includepolydiorganosiloxane polyamides and polydiorganosiloxane polyureas.

Polydiorganosiloxane polyamides have been prepared by condensationreactions of amino terminated silicones with short-chained dicarboxylicacids. Alternatively, these copolymers have been prepared bycondensation reactions of carboxy terminated silicones withshort-chained diamines. Because polydiorganosiloxanes (e.g.,polydimethylsiloxanes) and polyamides often have significantly differentsolubility parameters, it can be difficult to find reaction conditionsfor production of siloxane-based polyamides that result in high degreesof polymerization, particularly with larger homologs of thepolydiorganosiloxane segments. Many of the known siloxane-basedpolyamide copolymers contain relatively short segments of thepolydiorganosiloxane (e.g., polydimethylsiloxane) such as segmentshaving no greater than 30 diorganosiloxy (e.g., dimethylsiloxy) units orthe amount of the polydiorganosiloxane segment in the copolymer isrelatively low. That is, the fraction (i.e., amount based on weight) ofpolydiorganosiloxane soft segments in the resulting copolymers tends tobe low.

SUMMARY

Cyclic silazanes containing an oxamido ester group and methods of makingthese compounds are described. The compounds can be used, for example,to make oxamido ester-terminated siloxanes, which can be precursors forthe preparation of various polymeric materials such as, for example,polydiorganosiloxane polyoxamides.

In one aspect, the present disclosure provides a compound of Formula I:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is analkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo,or alkoxycarbonyl; and each R³, R⁴, and R⁵ is independently hydrogen oran alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo. Methods of making a compound of Formula I arealso disclosed herein.

In another aspect, the present disclosure also provides a method ofmaking a polymer precursor of Formula III:

The method includes combining under reaction conditions: a compound ofFormula I as described above and a silanol terminated siloxane ofFormula II:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; and n is aninteger of 0 to 1500.

In still another aspect, the present disclosure provides a method ofmaking a polymeric material including at least two repeat units ofFormula VIII:

wherein q is an integer greater than or equal to 2. The method includes(i) combining under reaction conditions: a compound of Formula I asdescribed above and a silanol terminated siloxane of Formula II:

to form a polymer precursor of Formula III:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is analkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo,or alkoxycarbonyl; each R³, R⁴, and R⁵ is independently hydrogen or analkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo; and n is an integer of 0 to 1500; and (ii)combining under reaction conditions the formed polymer precursor ofFormula III with one or more amine compounds having on average a formulaG(NHR⁶)_(r); wherein: G is a residue unit equal to the formulaG(NHR⁶)_(r) minus the r —NHR⁶ groups; R⁶ is hydrogen or alkyl (e.g., analkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R⁶ takentogether with G and with the nitrogen to which they are both attachedforms a heterocyclic group; and r is a number greater than or equal to2.

The presently disclosed polymeric materials can be conceived for use innumerous applications including, for example, in sealants, adhesives, asmaterial for fibers, as plastics additives, e.g., as impact modifiers orflame retardants, as material for defoamer formulations, as ahigh-performance polymer (thermoplastic, thermoplastic elastomer,elastomer), as packaging material for electronic components, ininsulating materials or shielding materials, in cable sheathing, inantifouling materials, as an additive for scouring, cleaning, orpolishing products, as an additive for body care compositions, as acoating material for wood, paper, and board, as a mold release agent, asa biocompatible material in medical applications such as contact lenses,as a coating material for textile fibers or textile fabric, as a coatingmaterial for natural substances such as leather and furs, for example,as a material for membranes and as a material for photoactive systems,for example, for lithographic techniques, optical data securement oroptical data transmission.

DEFINITIONS

The terms “comprises” and variations thereof do not have a limitingmeaning where these terms appear in the description and claims.

The words “preferred” and “preferably” refer to embodiments of theinvention that may afford certain benefits, under certain circumstances.However, other embodiments may also be preferred, under the same orother circumstances. Furthermore, the recitation of one or morepreferred embodiments does not imply that other embodiments are notuseful, and is not intended to exclude other embodiments from the scopeof the invention.

The terms “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

As used herein, the term “or” is generally employed in its senseincluding “and/or” unless the content clearly dictates otherwise.

The term “and/or” means one or all of the listed elements or acombination of any two or more of the listed elements.

The term “alkenyl” refers to a monovalent group that is a radical of analkene, which is a hydrocarbon with at least one carbon-carbon doublebond. The alkenyl can be linear, branched, cyclic, or combinationsthereof and typically contains 2 to 20 carbon atoms. In someembodiments, the alkenyl contains 2 to 18, 2 to 12, 2 to 10, 4 to 10, 4to 8, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkenyl groupsinclude ethenyl, n-propenyl, and n-butenyl.

The term “alkyl” refers to a monovalent group that is a radical of analkane, which is a saturated hydrocarbon. The alkyl can be linear,branched, cyclic, or combinations thereof and typically has 1 to 20carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples ofalkyl groups include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl,n-heptyl, n-octyl, and ethylhexyl.

The term “alkylene” refers to a divalent group that is a radical of analkane. The alkylene can be straight-chained, branched, cyclic, orcombinations thereof. The alkylene often has 1 to 20 carbon atoms. Insome embodiments, the alkylene contains 1 to 18, 1 to 12, 1 to 10, 1 to8, 1 to 6, or 1 to 4 carbon atoms. The radical centers of the alkylenecan be on the same carbon atom (i.e., an alkylidene) or on differentcarbon atoms.

The term “alkoxy” refers to a monovalent group of formula —OR where R isan alkyl group.

The term “alkoxycarbonyl” refers to a monovalent group of formula—(CO)OR where R is an alkyl group and (CO) denotes a carbonyl group withthe carbon attached to the oxygen with a double bond.

The term “aralkyl” refers to a monovalent group of formula —R³—Ar whereR^(a) is an alkylene and Ar is an aryl group. That is, the aralkyl is analkyl substituted with an aryl.

The term “aralkylene” refers to a divalent group of formula—R^(a)—Ar^(a)— where R^(a) is an alkylene and Ara is an arylene (i.e.,an alkylene is bonded to an arylene).

The term “aryl” refers to a monovalent group that is aromatic andcarbocyclic. The aryl can have one to five rings that are connected toor fused to the aromatic ring. The other ring structures can bearomatic, non-aromatic, or combinations thereof. Examples of aryl groupsinclude, but are not limited to, phenyl, biphenyl, terphenyl, anthryl,naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl,pyrenyl, perylenyl, and fluorenyl.

The term “arylene” refers to a divalent group that is carbocyclic andaromatic. The group has one to five rings that are connected, fused, orcombinations thereof. The other rings can be aromatic, non-aromatic, orcombinations thereof. In some embodiments, the arylene group has up to 5rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromaticring. For example, the arylene group can be phenylene.

The term “aryloxy” refers to a monovalent group of formula —OAr where Aris an aryl group.

The term “carbonyl” refers to a divalent group of formula —(CO)— wherethe carbon atom is attached to the oxygen atom with a double bond.

The term “halo” refers to fluoro, chloro, bromo, or iodo.

The term “haloalkyl” refers to an alkyl having at least one hydrogenatom replaced with a halo. Some haloalkyl groups are fluoroalkyl groups,chloroalkyl groups, or bromoalkyl groups.

The term “heteroalkylene” refers to a divalent group that includes atleast two alkylene groups connected by a thio, oxy, or —NR— where R isalkyl. The heteroalkylene can be linear, branched, cyclic, orcombinations thereof and can include up to 60 carbon atoms and up to 15heteroatoms. In some embodiments, the heteroalkylene includes up to 50carbon atoms, up to 40 carbon atoms, up to 30 carbon atoms, up to 20carbon atoms, or up to 10 carbon atoms. Some heteroalkylenes arepolyalkylene oxides where the heteroatom is oxygen.

The term “oxalyl” refers to a divalent group of formula —(CO)—(CO)—where each (CO) denotes a carbonyl group.

The terms “oxalylamino” and “aminoxalyl” are used interchangeably torefer to a divalent group of formula —(CO)—(CO)—NH— where each (CO)denotes a carbonyl.

The term “aminoxalylamino” refers to a divalent group of formula—NH—(CO)—(CO)—NR^(d)— where each (CO) denotes a carbonyl group and R^(d)is hydrogen, alkyl, or part of a heterocyclic group along with thenitrogen to which they are both attached. In most embodiments, R^(d) ishydrogen or alkyl. In many embodiments, R^(d) is hydrogen.

The term “polyvalent” refers to a group having a valence of greater than2.

The terms “polymer” and “polymeric material” refer to both materialsprepared from one monomer such as a homopolymer or to materials preparedfrom two or more monomers such as a copolymer, terpolymer, or the like.Likewise, the term “polymerize” refers to the process of making apolymeric material that can be a homopolymer, copolymer, terpolymer, orthe like. The terms “copolymer” and “copolymeric material” refer to apolymeric material prepared from at least two monomers.

The term “polydiorganosiloxane” refers to a divalent segment of formula

where each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; each Y isindependently an alkylene, aralkylene, or a combination thereof, andsubscript n is independently an integer of 0 to 1500.

The terms “room temperature” and “ambient temperature” are usedinterchangeably to mean temperatures in the range of 20° C. to 25° C.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numbers setforth are approximations that can vary depending upon the desiredproperties using the teachings disclosed herein.

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which can be used invarious combinations. In each instance, the recited list serves only asa representative group and should not be interpreted as an exclusivelist.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

Cyclic silazanes containing an oxamido ester group and methods of makingthese compounds are provided. The cyclic silazane compounds undergo ringopening reactions with hydroxy-functional molecules such as silanolterminated siloxanes. Thus, the cyclic silazanes can be used, forexample, to make oxamido ester-terminated siloxanes, which can be usedas precursors for the preparation of various polymeric materials suchas, for example, polydiorganosiloxane polyoxamides, which can be used toform a wide variety of compositions and articles. See, for example,copending applications with Attorney Docket Nos. 63217US002 entitled“BRANCHED POLYDIORGANOSILOXANE POLYAMIDE COPOLYMERS;” 63219US002entitled “POLYDIORGANOSILOXANE POLYAMIDE COPOLYMERS HAVING ORGANIC SOFTSEGMENTS;” 63284US002 entitled “MIXTURES OF POLYDIORGANOSILOXANEPOLYAMIDE-CONTAINING COMPONENTS AND ORGANIC POLYMERS;” and 6331 IUS002entitled “POLYDIORGANOSILOXANE POLYOXAMIDE COPOLYMERS”, all filed on thesame day herewith.

Cyclic Silazanes and Methods of Making Same

A cyclic silazane of Formula I is provided:

In this formula, each R¹ is independently an alkyl, haloalkyl, aralkyl,alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo. EachR² is independently an alkyl, haloalkyl, aryl, or aryl substituted withan alkyl, alkoxy, halo, or alkoxycarbonyl. Each R³, R⁴, and R⁵ isindependently hydrogen or an alkyl, haloalkyl, aralkyl, alkenyl, aryl,or aryl substituted with an alkyl, alkoxy, or halo.

Suitable alkyl groups for R¹, R³, R⁴, and/or R⁵ typically have 1 to 10carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Exemplaryalkyl groups include, but are not limited to, methyl, ethyl, isopropyl,n-propyl, n-butyl, and iso-butyl. Suitable haloalkyl groups for R¹, R³,R⁴, and/or R⁵ often have 3 to 10 carbon atoms and only a portion of thehydrogen atoms are replaced with a halogen. Exemplary haloalkyl groupsinclude chloroalkyl and fluoroalkyl groups with 1 to 3 halo atoms and 3to 10 carbon atoms. Suitable alkenyl groups for R¹, R³, R⁴, and/or R⁵often have 2 to 10 carbon atoms. Exemplary alkenyl groups often have 2to 10, 2 to 6, or 2 to 4 carbon atoms such as ethenyl, n-propenyl, andn-butenyl. Suitable aryl groups for R¹, R³, R⁴, and/or R⁵ often have 6to 12 carbon atoms. Phenyl is an exemplary aryl group. An aryl group canbe unsubstituted or substituted with an alkyl (e.g., an alkyl having 1to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), analkoxy (e.g., an alkoxy with 1 to 10 carbon atoms, 1 to 6 carbon atoms,or 1 to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro).Suitable aralkyl groups for R¹, R³, R⁴, and/or R⁵ usually have analkylene group having 1 to 10 carbon atoms and an aryl group with 6 to12 carbon atoms. In some exemplary aralkyl groups, the aryl group isphenyl and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbonatoms, or 1 to 4 carbon atoms (i.e., the structure of the aralkyl isalkylene-phenyl with phenyl bonded to an alkylene).

In some compounds of Formula I, at least one, and preferably both R¹groups are methyl. In some compounds of Formula I, at least one of R³,R⁴, and R⁵ are hydrogen, and preferably each of R³, R⁴, and R⁵ arehydrogen.

Suitable alkyl and haloalkyl groups for R² often have 1 to 10, 1 to 6,or 1 to 4 carbon atoms. Although tertiary alkyl (e.g., tert-butyl) andtertiary haloalkyl groups can be used, a primary or secondary carbonatom is often attached directly (i.e., bonded) to the adjacent oxygroup. Exemplary alkyl groups include methyl, ethyl, n-propyl,iso-propyl, n-butyl, and iso-butyl. Exemplary haloalkyl groups includechloroalkyl groups and fluoroalkyl groups in which some, but not all, ofthe hydrogen atoms on the corresponding alkyl group are replaced withhalo atoms. For example, the chloroalkyl or fluoroalkyl groups can bechloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl,4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,3-fluoropropyl, 4-fluorobutyl, and the like.

Suitable aryl groups for R² include those having 6 to 12 carbon atomssuch as, for example, phenyl. An aryl group can be unsubstituted orsubstituted with an alkyl (e.g., an alkyl having 1 to 4 carbon atomssuch as methyl, ethyl, or n-propyl), an alkoxy (e.g., an alkoxy having 1to 4 carbon atoms such as methoxy, ethoxy, or propoxy), halo (e.g.,chloro, bromo, or fluoro), or alkoxycarbonyl (e.g., an alkoxycarbonylhaving 2 to 5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, orpropoxycarbonyl).

Exemplary compounds according to Formula I include, but are not limitedto, those in which R¹ is methyl and in which R³, R⁴, and R⁵ are the same(e.g., hydrogen). R² can be an alkyl having 1 to 4 carbon atoms,haloalkyl having 1 to 4 carbon atoms, phenyl, phenyl substituted with analkoxycarbonyl having 2 to 5 carbon atoms, phenyl substituted with atleast one halo group, or phenyl substituted with an alkoxy having 1 to 4carbon atoms. In certain embodiments R² is ethyl.

Cyclic silazanes of Formula I can conveniently be made, for example, bycyclization of a compound of Formula VII:

wherein: each R¹, R², R³, R⁴, and R⁵ are as defined herein above for thecompound of Formula I. X represents a halogen, and preferably is Cl.

In some embodiments, the cyclization occurs in the presence of a base,preferably an organic base. Typically, a compound of Formula VII can bedissolved in an appropriate organic solvent, and a soluble organic basecan be added to result in the cyclization. A wide variety of organicsolvents can be used. Exemplary organic solvents include, but are notlimited to, tetrahydrofuran (THF), toluene, ethyl acetate,dichloromethane, and combinations thereof.

A wide variety of organic bases can be used. Exemplary organic basesinclude, but are not limited to, triethylamine (TEA), pyridine,N,N-dimethylaniline, N-methylimidazole, and combinations thereof.

Compounds of Formula VII can be conveniently made, for example, byhydrosilylation reactions. For example, a compound of Formula VII can bemade by reacting a compound of Formula VI:

with a hydrosilane of the formula (R¹)₂ClSiH in the presence of ahydrosilylation catalyst, wherein: each R¹, R², R³, R⁴, and R⁵ are asdefined herein above for the compound of Formula I. In certainembodiments reaction conditions include combining the compound ofFormula VI with the hydrosilane of the formula (R¹)₂ClSiH in anon-hydroxylic organic solvent in the presence of a platinum catalyst.

A wide variety of organic solvents can be used. Exemplary organicsolvents include, but are not limited to, toluene, tetrahydrofuran(THF), ethyl acetate, dichloromethane, and combinations thereof.

Typical platinum hydrosilylation catalysts include, for example,chloroplatinic acid and the bis(divinyltetramethyldisoloxane)platinumcomplex known as the Carswell catalyst. The reaction is preferablyconducted with excess hydrosilane (e.g., a 10-25% molar excess of thehydrosilane) using 0.05-1% by weight of Pt catalyst based on the totalweight of the compound of Formula VI and the hydrosilane. In someembodiments, the reaction can be conducted at ambient temperature andpressure. In some other embodiments, the reaction can be conducted at50° C. to 100° C. at elevated pressures in a pressure vessel.

Compounds of Formula VI can conveniently be made by combining an oxalateester of Formula IV:

and an allylamine of Formula V:

under conditions effective to form the oxalamic acid ester. In certainembodiments, effective reaction conditions include combining excessoxalate ester of Formula IV (e.g., a 1 to 5 fold molar excess of theoxalate ester of Formula IV) and the allylamine of Formula V either neator in an organic solvent. In some embodiments, the reaction can beconducted at ambient temperature and pressure. In some otherembodiments, the reaction can be conducted at elevated temperatures, andoptionally at elevated pressures in a pressure vessel. For embodimentsin which an organic solvent is used, a wide variety of organic solventscan be used. Exemplary organic solvents include, but are not limited to,diethylether, tetrahydrofuran (THF), toluene ethanol, ethyl acetate,dichloromethane, and combinations thereof.

Reaction of Cyclic Silazanes of Formula I with Silanol TerminatedSiloxanes

Cyclic silazanes of Formula I can be reacted with a silanol terminatedsiloxane of Formula II:

to give a polymer precursor of Formula III:

In silanol terminated siloxanes of Formula II, each R¹ is independentlyan alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo; and n is an integer of 0 to 1500.

In some compounds of Formula II, all R¹ groups can be one of alkyl,haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl,alkoxy, or halo (e.g., all R¹ Groups are an alkyl such as methyl or anaryl such as phenyl). In some compounds of Formula II, the R¹ groups aremixtures of two or more selected from the group consisting of alkyl,haloalkyl, aralkyl, alkenyl, aryl, and aryl substituted with an alkyl,alkoxy, or halo in any ratio. Thus, for example, in certain compounds ofFormula I, 0%, 1%, 2, %, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,90%, 95%, 98%, 99%, or 100% of the R¹ groups can be methyl; and 100%,99%, 98%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 2%, 1%,or 0% of the R¹ groups can be phenyl.

Each subscript n in Formulas II and III is independently an integer of 0to 1500. For example, subscript n can be an integer up to 1000, up to500, up to 400, up to 300, up to 200, up to 100, up to 80, up to 60, upto 40, up to 20, or up to 10. The value of n is often at least 1, atleast 2, at least 3, at least 5, at least 10, at least 20, or at least40. For example, subscript n can be in the range of 40 to 1500, 0 to1000, 40 to 1000, 0 to 500, 1 to 500, 40 to 500, 1 to 400, 1 to 300, 1to 200, 1 to 100, 1 to 80, 1 to 40, or 1 to 20.

Polymer precursors of Formula III can be prepared by combining a silanolterminated siloxane of Formula II with an amount of cyclic silazane ofFormula I that is greater than or equal to the molar equivalents ofsilanol groups. The reaction can be conducted either neat or in asuitable organic solvent at a temperature of 25 to 100° C. Suitablesolvents include, but are not limited to, tetrahydrofuran (THF),toluene, ethyl acetate, methylene chloride, and combinations thereof.

The polymer precursors of Formula III have groups of formulaR²—O—(CO)—(CO)—NH— at each end of the molecule. That is, the compoundshave at least two oxalylamino groups. Each R² is independently an alkyl,haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo, oralkoxycarbonyl. The group of formula R²O—(CO)—(CO)—NH— is analkoxyoxalylamino group when R² is an alkyl, a haloalkoxyoxalylaminogroup when R² is a haloalkyl, or an aryloxyoxalylamino group when R² isan unsubstituted or substituted aryl.

The compounds of Formula III can be used as precursors for thepreparation of various polymeric materials (e.g., elastomeric materials)including, for example, those described in U.S. patent application Ser.No. 11/317,271, filed 23 Dec. 2005. These polymeric materials can beused in various compositions including, for example, adhesivecompositions as described in U.S. patent application Ser. No.11/317,602, filed 23 Dec. 2005. These polymeric materials can be used invarious articles including, for example, films and multilayer films asdescribed in U.S. patent application Ser. Nos. 11/614,357 and11/614,169, both filed 21 Dec. 2006.

The compounds of Formula III, either alone or optionally in combinationwith other precursor materials (e.g., other precursor materials havingoxamido ester-terminated segments such as those including amideend-capped (e.g., oxalated) organic soft segments), can be reacted withone or more amine compounds to form linear and/or branched polymers.

For example, the compounds can undergo a condensation reaction whencombined with one or more amine compounds having on average a formulaG(NHR⁶)_(r); wherein: G is a residue unit equal to the formulaG(NHR⁶)_(r) minus the r —NHR⁶ groups; and r is a number greater than orequal to 2, to give a polymeric material having at least two repeatunits of Formula VIII:

wherein q is an integer greater than or equal to 2. In certainembodiments q can, for example, be equal to 2, 3, or 4. The one or moreamine compounds are typically on average of the formula G(NHR⁶), where ris a number greater than or equal to 2. Group R⁶ is hydrogen or alkyl(e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R⁶taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group (e.g., R⁶HN-G-NHR⁶ is piperazine).In most embodiments, R⁶ is hydrogen or an alkyl. In many embodiments,all of the amino groups of the one or more amine compounds are primaryamino groups (i.e., all the R⁶ groups are hydrogen) and the one or moreamine compounds are of the formula G(NH₂)_(q) (e.g., a diamine of theformula R⁶HN-G-NHR⁶ when q=2). The R²OH by-product is typically removedfrom the resulting polydiorganosiloxane polyamide.

In certain embodiments, the one or more amine compounds are a mixture of(i) a diamine compound of formula R⁶HN-G-NHR⁶ and (ii) a polyaminecompound of formula G(NHR⁶)_(q), where q is an integer greater than 2.In such embodiments, the polyamine compound of formula G(NHR⁶)_(q) canbe, but is not limited to, triamine compounds (i.e., q=3), tetraaminecompounds (i.e., q=4), and combinations thereof. In such embodiments,the number of equivalents of polyamine (ii) per equivalent of diamine(i) is preferably at least 0.001, more preferably at least 0.005, andmost preferably at least 0.01. In such embodiments, the number ofequivalents of polyamine (ii) per equivalent of diamine (i) ispreferably at most 3, more preferably at most 2, and most preferably atmost 1.

Exemplary triamines include, but are not limited to,tris(2-aminoethyl)amine, diethylentriamine, polyoxyalkylene triaminessuch as those available, for example, from Huntsman (The Woodlands,Tex.) under the trade designations JEFFAMINE T-3000 (i.e.,polyoxypropropylene triamine having an average molecular weight of 3000g/mole) and JEFFAMINE T-5000 (i.e., polyoxypropropylene triamine havingan average molecular weight of 5000 g/mole), amino-functionalpolysiloxanes, and combinations thereof. Exemplary tetraamines include,but are not limited to, triethylene tetraamine. Exemplarypolydimethylsiloxanes having amino functionality include, for example,polydimethylsiloxane copolymers having aminopropylmethylsiloxane unitssuch as those available under the trade designations AMS-132, AMS-152,and AMS-162 from Gelest, Inc., Morrisville, Pa.

When the one or more amine compounds include diamines, the diamines aresometimes classified as organic diamines or polydiorganosiloxanediamines with the organic diamines including, for example, thoseselected from alkylene diamines, heteroalkylene diamines, arylenediamines, aralkylene diamines, or alkylene-aralkylene diamines. Tertiaryamines that do not react with the precursor of Formula II (II-a or II-b)can be present. Additionally, the diamine is free of any carbonylaminogroup. That is, the diamine is not an amide.

Exemplary polyoxyalkylene diamines (i.e., G is a heteroalkylene with theheteroatom being oxygen) include, but are not limited to, thosecommercially available from Huntsman, The Woodlands, Tex. under thetrade designation JEFFAMINE D-230 (i.e., polyoxypropropylene diaminehaving an average molecular weight of 230 g/mole), JEFFAMINE D-400(i.e., polyoxypropylene diamine having an average molecular weight of400 g/mole), JEFFAMINE D-2000 (i.e., polyoxypropylene diamine having anaverage molecular weight of 2,000 g/mole), JEFFAMINE HK-511 (i.e.,polyetherdiamine with both oxyethylene and oxypropylene groups andhaving an average molecular weight of 220 g/mole), JEFFAMINE ED-2003(i.e., polypropylene oxide capped polyethylene glycol having an averagemolecular weight of 2,000 g/mole), and JEFFAMINE EDR-148 (i.e.,triethyleneglycol diamine).

Exemplary alkylene diamines (i.e., G is a alkylene) include, but are notlimited to, ethylene diamine, propylene diamine, butylene diamine,hexamethylene diamine, 2-methylpentamethylene 1,5-diamine (i.e.,commercially available from DuPont, Wilmington, Del. under the tradedesignation DYTEK A), 1,3-pentane diamine (commercially available fromDuPont under the trade designation DYTEK EP), 1,4-cyclohexane diamine,1,2-cyclohexane diamine (commercially available from DuPont under thetrade designation DHC-99), 4,4′-bis(aminocyclohexyl)methane, and3-aminomethyl-3,5,5-trimethylcyclohexylamine.

Exemplary aralkylene diamines (i.e., G is an aralkylene such asalkylene-phenyl) include, but are not limited to4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e.,G is an alkylene-aralkylene such as alkylene-phenylene-alkylene)include, but are not limited to, 4-aminomethyl-benzylamine,3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.

The following exemplary embodiments are provided by the presentdisclosure:

Embodiment 1

A compound of Formula I:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is analkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo,or alkoxycarbonyl; and each R³, R⁴, and R⁵ is independently hydrogen oran alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo.

Embodiment 2

The compound of embodiment 1 wherein each R¹ is methyl.

Embodiment 3

The compound of embodiment 1 or 2 wherein R² is an alkyl having 1 to 4carbon atoms or a haloalkyl having 1 to 4 carbon atoms, the alkyl orhaloalkyl having a primary carbon atom or secondary carbon atom bondedto the adjacent oxy group.

Embodiment 4

The compound of any of embodiments 1 to 3 wherein R² is ethyl.

Embodiment 5

The compound of embodiment 1 or 2 wherein R² is a phenyl or a phenylsubstituted with an alkyl having 1 to 4 carbon atoms, with an alkoxyhaving 1 to 4 carbon atoms, with a halo, or with an alkoxycarbonylhaving 2 to 5 carbon atoms.

Embodiment 6

The compound of any of embodiments 1 to 5 wherein each R³, R⁴, and R⁵ ishydrogen.

Embodiment 7

The compound of any of embodiments 1 to 5 wherein each R³, R⁴, and R⁵ isan alkyl having 1 to 4 carbon atoms or a haloalkyl having 1 to 4 carbonatoms.

Embodiment 8

A method of making a polymer precursor of Formula III:

the method comprising combining under reaction conditions: a compoundaccording to any of embodiments 1 to 7; and a silanol terminatedsiloxane of Formula II:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; and n is aninteger of 0 to 1500.

Embodiment 9

The method of embodiment 8 wherein each R¹ is methyl.

Embodiment 10

A method of making a polymeric material comprising at least two repeatunits of Formula VIII:

wherein q is an integer greater than or equal to 2, the methodcomprising combining under reaction conditions: a compound according toany of embodiments 1 to 7; and a silanol terminated siloxane of FormulaII:

to form a polymer precursor of Formula III:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is analkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo,or alkoxycarbonyl; each R³, R⁴, and R⁵ is independently hydrogen or analkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo; and n is an integer of 0 to 1500; and combiningunder reaction conditions the formed polymer precursor of Formula IIIwith one or more amine compounds having on average a formulaG(NHR⁶)_(r); wherein: G is a residue unit equal to the formulaG(NHR⁶)_(r) minus the r —NHR⁶ groups; R⁶ is hydrogen or alkyl or R⁶taken together with G and with the nitrogen to which they are bothattached forms a heterocyclic group; and r is a number greater than orequal to 2.

Embodiment 11

The method of embodiment 10 wherein each R¹ is methyl.

Embodiment 12

A method of making a compound of Formula I, the method comprising:subjecting a compound of Formula VII to conditions effective to causecyclization:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl,aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is analkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo,or alkoxycarbonyl; each R³, R⁴, and R⁵ is independently hydrogen or analkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with analkyl, alkoxy, or halo; and X is a halogen.

Embodiment 13

The method of embodiment 12 wherein conditions effective to causecyclization comprise providing an organic base.

Embodiment 14

The method of embodiment 13 wherein the organic base is provided in asolvent.

Embodiment 15

The method of embodiment 13 or 14 wherein the organic base istriethylamine.

Embodiment 16

The method of any of embodiments 12 to 15 wherein each R¹ is methyl.

Embodiment 17

The method of any of embodiments 12 to 16 wherein R² is an alkyl having1 to 4 carbon atoms or a haloalkyl having 1 to 4 carbon atoms, the alkylor haloalkyl having a primary carbon atom or secondary carbon atombonded to the adjacent oxy group.

Embodiment 18

The method of any of embodiments 12 to 17 wherein R² is ethyl.

Embodiment 19

The method of any of embodiments 12 to 16 wherein R² is a phenyl or aphenyl substituted with an alkyl having 1 to 4 carbon atoms, with analkoxy having 1 to 4 carbon atoms, with a halo, or with analkoxycarbonyl having 2 to 5 carbon atoms.

Embodiment 20

The method of any of embodiments 12 to 19 wherein each R³, R⁴, and R⁵ ishydrogen.

Embodiment 21

The method of any of embodiments 12 to 19 wherein each R³, R⁴, and R⁵ isan alkyl having 1 to 4 carbon atoms or a haloalkyl having 1 to 4 carbonatoms.

Embodiment 22

The method of any of embodiments 12 to 21 wherein X is Cl.

The foregoing describes the invention in terms of embodiments foreseenby the inventors for which an enabling description was available,notwithstanding that insubstantial modifications of the invention, notpresently foreseen, may nonetheless represent equivalents thereto.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, and the like in the examples are by weight, unlessnoted otherwise. Solvents and other reagents used were obtained fromSigma-Aldrich Chemical Company; Milwaukee, Wis. unless otherwise noted.

Preparative Example 1 N-Allylamido Ethyl Oxalate

Diethyl oxalate (256.00 grams) was charged to a round bottom flask andcooled to 0-5° C., and 50 g allylamine was added slowly to the stirredsolution. The reaction was allowed to warm to ambient temperature. Aftermixing overnight, ethanol and the excess diethyl oxalate were removedunder reduced pressure. The residue was distilled in vacuo and theproduct collected as a clear, colorless liquid (boiling point 72-76° C.,1 Torr), and the yield was 111 grams.

Preparative Example 2 3-(Chlorodimethylsilyl propylamido) ethyl oxalate

A glass pressure vessel was charged with 22.58 g ofchlorodimethylsilane, 30.00 g of N-allylamido ethyl oxalate as preparedin Preparative Example 1, and 4 drops of a 2.3% solution ofbis(divinyltetramethyldisoloxane)platinum complex (i.e., Pthydrosilation catalyst. The vessel was sealed and heated to 70-80° C.for 16 hours. The clear, yellow liquid was cooled to ambienttemperature, the residual pressure slowly released, and the contentsreheated with stirring to 80° C. to remove excess chlorodimethylsilane.Gas chromatographic analysis revealed the presence of only approximately5% unreacted N-allylamido ethyl oxalate starting material, and the yieldwas 49 grams.

Example 1 N-Ethyl Oxalyl Aza Sila Cyclopentane Formula I with R¹=R²=R³=H

The crude product from Preparative Example 2 was dissolved in 110 g oftoluene. Triethylamine, 21.10 g, was added dropwise with stirring, and acopious precipitate immediately formed. After 16 hours, the mixture wasfiltered through a fritted glass funnel under nitrogen pressure, thefilter cake washed with additional toluene, and the solvent removed on arotary evaporator under reduced pressure. The residue was distilled invacuo, and the cyclic silazane isolated as a clear, colorless liquid(boiling point 84° C., 1 Torr). The yield was 32.55 g (89%). NMRanalysis confirmed the structure as the cyclic silazane indicated inFormula I with R¹=R²=R³=H.

Example 2 Conversion of a Silanol Terminated Silicone into N-EthylOxalamidopropyl Terminated Silicone

A 4200 MW silanol terminated silicone fluid (71.68 g) was heated undervacuum at 100° C. for 10 minutes and then cooled to ambient temperatureunder nitrogen. A cyclic silazane of Formula I with R¹=R²=R³=H and asprepared in Example 1 (3.86 grams) was added and the contents stirred at50° C. for 0.5 hour. Gas chromatographic analysis showed the completedisappearance of the cyclic silazane. An additional 3.86 grams of cyclicsilazane of Formula I with R¹=R²=R³=H was added, and heating continueduntil the silazane was no longer consumed. The product was heated undervacuum at 150° C. (1 Torr) to completely remove any unreacted cyclicsilazane and then cooled to ambient temperature. NMR analysis revealedthat 100% of the silanol chain ends had been converted into the ethyloxalyl amidopropyl chain ends.

Example 3 Preparation of a Silicone Polyoxamide

N-Ethyl oxalamidopropyl terminated silicone as prepared in Example 2(10.0 grams) was charged to a 4 ounce wide mouth jar with rapidstirring, and ethylene diamine (0.13 gram) was quickly added. Afterapproximately 30 seconds, the reaction had solidified to a frothy solid.After 24 hours, the product was dissolved in 40 ml of THF over another24 hour period. The viscous solution was cast into a glass Petri dishand the solvent allowed to evaporate to dryness to provide a clear, verystrong elastomeric film of the silicone polyoxamide.

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1. A method of making a polymer precursor of Formula III:

the method comprising combining under reaction conditions: a compound of Formula I:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is an alkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl; and each R³, R⁴, and R⁵ is independently hydrogen or an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; and a silanol terminated siloxane of Formula II:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; and n is an integer of 0 to
 1500. 2. The method of claim 1 wherein each R¹ is methyl.
 3. A method of making a polymeric material comprising at least two repeat units of Formula VIII:

wherein q is an integer greater than or equal to 2, the method comprising combining under reaction conditions: a compound of Formula I:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is an alkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl; and each R³, R⁴, and R⁵ is independently hydrogen or an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; and a silanol terminated siloxane of Formula II:

to form a polymer precursor of Formula III:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is an alkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl; each R³, R⁴, and R⁵ is independently hydrogen or an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; and n is an integer of 0 to 1500; and combining under reaction conditions the formed polymer precursor of Formula III with one or more amine compounds having on average a formula G(NHR⁶)_(r); wherein: G is a residue unit equal to the formula G(NHR⁶)_(r) minus the r —NHR⁶ groups; R⁶ is hydrogen or alkyl or R⁶ taken together with G and with the nitrogen to which they are both attached forms a heterocyclic group; and r is a number greater than or equal to
 2. 4. The method of claim 3 wherein each R¹ is methyl.
 5. A method of making a compound of Formula I, the method comprising: subjecting a compound of Formula VII to conditions effective to cause cyclization:

wherein: each R¹ is independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; R² is an alkyl, haloalkyl, aryl, or aryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl; each R³, R⁴, and R⁵ is independently hydrogen or an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo; and X is a halogen.
 6. The method of claim 5 wherein conditions effective to cause cyclization comprise providing an organic base.
 7. The method of claim 6 wherein the organic base is provided in a solvent.
 8. The method of claim 6 wherein the organic base is triethylamine.
 9. The method of claim 5 wherein each R¹ is methyl.
 10. The method of claim 5 wherein R² is an alkyl having 1 to 4 carbon atoms or a haloalkyl having 1 to 4 carbon atoms, the alkyl or haloalkyl having a primary carbon atom or secondary carbon atom bonded to the adjacent oxy group.
 11. The method of claim 10 wherein R² is ethyl.
 12. The method of claim 5 wherein R² is a phenyl or a phenyl substituted with an alkyl having 1 to 4 carbon atoms, with an alkoxy having 1 to 4 carbon atoms, with a halo, or with an alkoxycarbonyl having 2 to 5 carbon atoms.
 13. The method of claim 5 wherein each R³, R⁴, and R⁵ is hydrogen.
 14. The method of claim 5 wherein each R³, R⁴, and R⁵ is an alkyl having 1 to 4 carbon atoms or a haloalkyl having 1 to 4 carbon atoms.
 15. The method of claim 5 wherein X is Cl. 